29,541 results match your criteria Inorganic chemistry[Journal]


Tubelike Uranyl-Phenylenediacetate Assemblies from Screening of Ligand Isomers and Structure-Directing Counterions.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

ISIS , Université de Strasbourg , 8 allée Gaspard Monge , 67083 Strasbourg , France.

Reaction of 1,2-, 1,3-, or 1,4-phenylenediacetic acids (1,2-, 1,3-, or 1,4-HPDA) with uranyl ions under solvo-hydrothermal conditions and in the presence of [M(L) ] cations, in which M = transition metal cation, L = 2,2'-bipyridine (bipy) or 1,10-phenanthroline (phen), n = 2 or 3, and q = 1 or 2, gave 10 complexes which have been crystallographically characterized. The diacetate ligands are bis-chelating and the uranyl cations are tris-chelated in all cases. [UO(1,2-PDA)Zn(phen)]·2HO (1) and [UO(1,4-PDA)Mn(bipy)]·HO (2) are heterometallic, neutral one-dimensional (1D) coordination polymers in which the carboxylate-coordinated 3d block metal cation is either decorating only (1) or participates in polymer building (2). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00804DOI Listing

Comparing the Ligand Behavior of N-Heterocyclic Phosphenium and Nitrosyl Units in Iron and Chromium Complexes.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Institute for Inorganic Chemistry , University of Stuttgart , Pfaffenwaldring 55 , 70550 Stuttgart , Germany.

N-Heterocyclic phosphenium (NHP) and nitrosonium (NO) ligands are often viewed as isolobal analogues that share the capability to switch between different charge states and thus display redox "noninnocent" behavior. We report here on mixed complexes [(NHP)M(CO) (NO)] (M = Fe, Cr; n = 2, 3), which permit evaluating the donor/acceptor properties of both types of ligands and their interplay in a single complex. The crystalline target compounds were obtained from reactions of N-heterocyclic phosphenium triflates with PPN[Fe(CO)(NO)] or PPN[Cr(CO)(NO)], respectively, and fully characterized (PPN = nitride-bistriphenylphosphonium cation). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00737DOI Listing

Photoinduced Intercomponent Processes in Selectively Addressable Bichromophoric Dyads Made of Linearly Arranged Ru(II) Terpyridine and Expanded Pyridinium Components.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Univ Paris Diderot , Sorbonne Paris Cité, ITODYS, UMR CNRS 7086 , 15 rue J-A de Baïf , 75013 Paris , France.

Three new linearly arranged bichromophoric systems 1-3 have been prepared, and their photophysical properties have been studied, taking also advantage of femtosecond pump-probe transient absorption spectroscopy. The three compounds contain the same chromophores, that is a Ru(II)-terpy-like species and a fused expanded bipyridinium (FEBP) unit, separated by three different, variously methylated biphenylene-type bridges. The chromophores have been selected to be selectively addressable, and excitation involving the Ru-based or the FEBP-based dyes results in different excited-state decays. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00139DOI Listing

Synthesis, Crystal Structures, and Photochemical Properties of a Family of Heterometallic Titanium Oxo Clusters.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

State Key Laboratory of Rare Earth Resource Utilization , Changchun Institute of Applied Chemistry, Chinese Academy of Sciences , 5625 Renmin Street , Changchun , Jilin 130022 , China.

The incorporation of heterometallic atoms into the structure of titanium-oxygen nanomaterials is one of the known and effective strategies to develop new high-performance photovoltaic active materials. In this study, we have synthesized three benzoic acid-stabilized heterometallic titanium oxo clusters with the different transition metals Co, Cu, and Cd, formulated as [TiCo(μ-O)(μ-O)(CHCOO)(CHCN)]·2CHCN (1), [TiCu(μ-O)(CHCOO)] (2), and [TiCd(μ-O)(μ-O)(μ-O)(CHCOO)(CHCOOH)(CHCN)]·CHCN·CHCOOH (3), and then we characterized their structures. UV-vis spectroscopy analysis revealed an enhanced UV-vis-light absorption of those heterometallic clusters. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00508DOI Listing

11/15/17 Complexes as Molecular Models for Metal Halide Double Perovskite Materials.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Department of Chemistry and Material Sciences Center , Philipps-Universität Marburg , Hans-Meerwein-Straße , 35043 Marburg , Germany.

Thirteen neutral complexes [E M X (PPh) (L) ] (E = Bi, Sb; M = Cu, Ag; X = Cl, Br, I; L = solvent) featuring three different motifs were prepared and characterized regarding their structure, stability, and absorption spectra. While not identical in structural motif, the compounds can serve as models for the influence of the composition E/M/X on the optical properties of double perovskites AEMX (A = Cs, CHNH). Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00429
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http://dx.doi.org/10.1021/acs.inorgchem.9b00429DOI Listing
April 2019
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Synthesis and Reactivity of a Hypersilylsilylene.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Academy of Scientific and Innovative Research , Ghaziabad 201002 , India.

Stabilization of an amidinatosilylene with a bulky tris(trimethylsilyl)silyl substituent was realized with the preparation of PhC(N tBu)Si{Si(SiMe)} (1) from PhC(N tBu)SiHCl with K{Si(SiMe)} in more than 90% yield. The highly deshielded Si NMR resonance (δ = 76.91 ppm) can be attributed to the absence of a π-donating substituent. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00418DOI Listing

Adjustable Magnetic Phase Transition Inducing Unusual Zero Thermal Expansion in Cubic RCo-Based Intermetallic Compounds (R = Rare Earth).

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Beijing Advanced Innovation Center for Materials Genome Engineering, Department of Physical Chemistry, and State Key Laboratory of Advanced Metals and Materials , University of Science and Technology Beijing , Beijing 100083 , China.

Metallic materials that exhibit negligible thermal expansion or zero thermal expansion (ZTE) have great merit for practical applications, but these materials are rare and their thermal expansions are difficult to control. Here, we successfully tailored the thermal expansion behaviors from strongly but abruptly negative to zero over wide temperature ranges in a series of (Gd,R)(Co,Fe) (R = Dy, Ho, Er) intermetallic compounds by tuning the composition to bring the first-order magnetic phase transition to second-order. Interestingly, an unusual isotropic ZTE property with a coefficient of thermal expansion of α = 0. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00480DOI Listing

Pore Space Partitioning of Metal-Organic Framework for CH Separation from Methane.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

School of Materials Science and Chemical Engineering , Ningbo University , Ningbo 315211 , China.

To develop efficient adsorbent materials for CH separation from methane, herein, we design a new 3-D framework (NbU-5) using the pore space partition strategy: Zn(OCR) paddlewheel units connect tetra-carboxylic linkers to build a primary framework, and 4,4-bipyridine, which acts as a pore-partitioning agent, has been successfully inserted into the cage of the primary framework. Remarkably, NbU-5 exhibits excellent CH/CH and CH/CH selectivity, which is proved by breakthrough experiments. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00550DOI Listing

Searching for the Optimized Luminescent Lanthanide Phosphor Using Heuristic Algorithms.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry , Chinese Academy of Sciences , Changchun 130022 , China.

In this research, four heuristic algorithms (HAs), including simulated annealing (SA), improved annealing with a harmony search algorithm (HSA), particle swarm optimization (PSO), and genetic algorithm (GA), were used to optimize the luminescent intensity of phosphor. Among the four HAs, the improved algorithm HSA got better phosphors than SA (without using the known coded concentration). The PSO algorithm got gradually better results with increased generation, and the GA could find the best local phosphors with shorter time. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00667DOI Listing

Inclusion of Ln(III) in the Complexes of Co(II) with a Mannich Base Ligand: Development of Atmospheric CO Fixation and Enhancement of Catalytic Oxidase Activities.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Department of Chemistry, University College of Science , University of Calcutta , 92, A. P. C. Road , Kolkata 700009 , West Bengal , India.

The reaction of the Mannich base ligand (HL = N, N'-dimethyl- N, N'-bis(2-hydroxy-3-methoxy-5-methylbenzyl)ethylenediamine) with Co(OAc)·4HO and Ln(III) nitrate salts (Ln = Gd, Tb, and Dy) under basic conditions afforded three carbonato-bridged isostructural tetranuclear heterometallic Co(II)-Ln(III) complexes (CoGdL(μ-CO)(NO)] (1), [CoTbL(μ-CO)(NO)] (2), and [CoDyL(μ-CO)(NO)] (3)) by atmospheric CO fixation. In all structures, two dinuclear [(CoL)Ln(NO)] units are linked via two μ-carbonato groups to form the tetranuclear CoLn core. The geometry around two penta-coordinated Co(II) ions is distorted square pyramid, and that around two nona-coordinated Ln(III) ions is intermediate between "spherical tricapped trigonal prism" and "spherical capped square antiprism" in all complexes. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00121DOI Listing

Zirconium-Nitrogen Intermolecular Frustrated Lewis Pairs.

Inorg Chem 2019 Apr 24. Epub 2019 Apr 24.

Cardiff Catalysis Institute, School of Chemistry , Cardiff University , Main Building, Park Place , Cardiff , CF10 3AT , United Kingdom.

A series of intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene alkoxide complexes ([CpZr(OMes)] 1 or ([Cp*Zr(OMes)] 2) with nitrogen Lewis bases (NEt, NEtPr, pyridine, 2-methylpyridine, 2,6-lutidine) are reported. The interaction between Zr and N depends on the specific derivatives used, in general more sterically encumbered pairs leading to a more frustrated interaction; however, DOSY NMR spectroscopy reveals these interactions to be dynamic in nature. The pairs undergo typical FLP-type reactivity with D, CO, THF, and PhCCD. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00569DOI Listing

Trends in Synthesis, Crystal Structure, and Thermal and Magnetic Properties of Rare-Earth Metal Borohydrides.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Center for Materials Crystallography, Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry , Aarhus University , Langelandsgade 140 , 8000 Aarhus C , Denmark.

Synthesis, crystal structures, and thermal and magnetic properties of the complete series of halide-free rare-earth (RE) metal borohydrides are presented. A new synthesis method provides high yield and high purity products. Fifteen new metal borohydride structures are reported. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03258DOI Listing

Crystal Structure and Photoluminescence Properties of an Incommensurate Phase in EuO- and PO-Doped CaSiO.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Department of Life Science and Applied Chemistry , Nagoya Institute of Technology , Nagoya 466-8555 , Japan.

We have for the first time clarified the incommensurately modulated crystal structure as well as the photoluminescence properties of Eu-activated CaSiO solid solution, the chemical formula of which is (CaEu□)(SiP)O, where □ denotes vacancies in Ca sites with the replacement of Si by P. The emission spectrum upon the 335 nm excitation showed a relatively broad band centered at ca. 490 nm and a full width at half-maximum of ca. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00408DOI Listing

Redox-Active Zeolitic Transition Metal Oxides Based on ε-Keggin Units for Selective Oxidation.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Faculty of Engineering , Kanagawa University , Rokkakubashi, Kanagawa-ku, Yokohama-shi , Kanagawa 221-8686 , Japan.

The design and development of zeolitic transition metal oxides for selective oxidation are interesting due to the combination of the redox properties and microporosities. Redox-active zeolitic transition metal oxides based on ε-Keggin iron molybdates were synthesized. O can be activated by the materials via an electron-transfer-based process, and the materials can be oxidized even at room temperature. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00502DOI Listing

X-ray Absorption Spectroscopy Investigations of Copper(II) Coordination in the Human Amyloid β Peptide.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Molecular and Environmental Sciences Group, Department of Geological Sciences , University of Saskatchewan , 114 Science Place , Saskatoon , Saskatchewan S7N 5E2 , Canada.

Alzheimer's disease (AD) is the main cause of age-related dementia and currently affects approximately 5.7 million Americans. Major brain changes associated with AD pathology include accumulation of amyloid beta (Aβ) protein fragments and formation of extracellular amyloid plaques. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00507DOI Listing

Size-Driven Stability of Lanthanide Thiophosphates Grown from an Iodide Flux.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

To determine the influence of the lanthanide size on the structures and properties of thiophosphates, a thiophosphate series containing different lanthanides was synthesized via high temperature flux crystal growth and their structures and physical properties analyzed and compared. Layered thiohypophosphates NaLnPS (Ln = La, Ce, Pr) and thiopyrophosphates CsLnPS (Ln = Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Yb, Y) were grown out of an iodide flux using consistent reaction conditions across both series. Under the mildly reducing iodide flux reaction conditions, a rather rare example of phosphorus reduction from the +5 to the +4 oxidation state was observed. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00806
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http://dx.doi.org/10.1021/acs.inorgchem.9b00806DOI Listing
April 2019
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1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)SCH Substituent and Reaction Conditions on the Architecture of the 0D-3D Networks.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Institut UTINAM, UMR CNRS 6213, 16 Route de Gray , Université Bourgogne Franche-Comté , 25030 Besançon , France.

The parent compound 1,3-dithiane (L1) was reacted with CuI providing the 1D coordination polymer [{Cu(μ-I)Cu}(μ-L1)] (CP1), an isostructural compound [{Cu(μ-Br)Cu}(μ-L1)] (CP2) was isolated upon treatment of CuBr with L1. In contrast, treatment of L1 with CuCl results in the formation of 2D polymeric [{Cu(μ-Cl)Cu}(μ-L1)] (CP3), in which each sulfur atom acts as a 4-electron donor. The 1D compounds [{Cu(μ-X)Cu}(μ-L2)] (CP7, X = Br, and CP8, X = Cl) resulting from treatment of 2-methyl-1,3 dithiane (L2) with CuBr and CuCl are isostructural with their CuI homologue [{Cu(μ-I)Cu}(μ-L2)] (CP5), reported previously. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00114DOI Listing

Targeting Energy Metabolism by a Platinum(IV) Prodrug as an Alternative Pathway for Cancer Suppression.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

State Key Laboratory of Pharmaceutical Biotechnology, School of Life Sciences , Nanjing University , Nanjing 210023 , P.R. China.

Cancer is characterized by abnormal cellular energy metabolism, which preferentially switches to aerobic glycolysis rather than oxidative phosphorylation as a means of glucose metabolism. Many key enzymes involved in the abnormal glycolysis are potential targets of anticancer drugs. Platinum(IV) complexes are potential anticancer prodrugs and kinetically more inert than the platinum(II) counterparts, which offer an opportunity to be modified by functional ligands for activation or targeted delivery. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00708
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http://dx.doi.org/10.1021/acs.inorgchem.9b00708DOI Listing
April 2019
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A Pyrene-Functionalized Metal-Organic Framework for Nonenzymatic and Ratiometric Detection of Uric Acid in Biological Fluid via Conformational Change.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Department of Chemistry , Indian Institute of Technology Guwahati , Guwahati , 781039 , Assam , India.

In this work, a water-stable, pyrene-functionalized Hf-based mixed-ligand metal-organic framework (MOF) with UiO-66 (UiO = University of Oslo) framework topology was designed and synthesized for the fluorimetric detection of uric acid (UA) in aqueous medium. The free pyrene-functionalized ligand changes its conformation (monomer to excimer) upon framework formation, which was confirmed via fluorescence spectral studies. The MOF material showed a fast, selective, sensitive (detection limit 1. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03629DOI Listing

Enhanced Electrocatalytic Activity of Trace Pt in Ternary CuCoPt Alloy Nanoparticles for Hydrogen Evolution.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering , College of Chemistry, Beijing University of Chemical Technology , Beijing 100029 , China.

We report an enhanced high electrocatalytic hydrogen evolution activity of trace Pt and Co diluted in ternary CuCoPt alloy nanoparticles with Cu as the substrate. Using only 10% Pt atoms can display even better activity and stability in hydrogen evolution reactions than using pure Pt nanoparticles. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00694
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http://dx.doi.org/10.1021/acs.inorgchem.9b00694DOI Listing
April 2019
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Luminescent Di- and Tetranuclear Gold Complexes of Bis(diphenylphosphinyl)-Functionalized Dipyrido-Annulated N-Heterocyclic Carbene.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Department of Applied Chemistry, Graduate School of Engineering , Hiroshima University , Higashi-Hiroshima 7398527 , Japan.

Phosphine-functionalized N-heterocyclic carbene (NHC) ligands are known to complex group 11 metal centers to form multinuclear complexes with photoluminescence properties. This study reports a structurally rigid ortho-substituted dipyrido-annulated NHC with T-shape coordination geometry and its di- and tetranuclear gold(I) complexes. The free ligand as well as all metal complexes are found luminescent at room temperature and phosphorescent at 77 K. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00514
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http://dx.doi.org/10.1021/acs.inorgchem.9b00514DOI Listing
April 2019
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α-AgVO Decorated by Hydroxyapatite (Ca(PO)(OH)): Tuning Its Photoluminescence Emissions and Bactericidal Activity.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Departamento de Química , CDMF, Universidade Federal de São Carlos (UFSCar) , 13565-905 São Carlos , São Paulo , Brazil.

Defect-related luminescent materials have attracted interest because of their excellent optical properties and are considered as a less expensive and nontoxic alternative to commonly used lanthanide-based optical systems. These materials are fundamentally and technologically important for the next generation of full-color tunable light-emitting diodes as well as in the biomedical field. In this study, we report the preparation of α-silver vanadate (α-AgVO, AV) decorated by hydroxyapatite (Ca(PO)(OH), HA) with intense photoluminescence (PL) emissions at various HA/AV molar ratios (1:1-1:1/32) by a simple route based on chemical precipitation. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00249DOI Listing

Halogen and Sulfur Oxidation of Germanium and Tin Dications.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

X-ray Crystallography Laboratory, Department of Chemistry , University of Alberta , Edmonton , AB T6G 2G2 , Canada.

Herein we present the oxidation of base-stabilized tetrel dications [LM][OTf] [L = BIMEt = tris(1-ethyl-benzoimidazol-2-ylmethyl)amine and M = Ge, Sn] with PCl, SeCl, Br, and I to access dicationic dihalides [LMX][OTf]. The addition of oxygen-rich donor molecules (picoline N-oxide, OPEt) to dications [LM][OTf] yielded donor-acceptor complexes bearing a tetrel(II) dication adjacent to a pnictogen(V) moiety. The addition of elemental sulfur to [LGe][OTf] yielded [(LGeS)][OTf] containing a dimeric tetracation. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00419DOI Listing

High Selectivity of Hydrogenation Reaction over Co@C/PC Catalyst at Room Temperature.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, School of Chemistry and Chemical Engineering , Hunan University of Science and Technology , Xiangtan 411201 , China.

In the field of catalysis, material scientists pay much attention to tuning the activity and chemoselectivity of metal nanoparticles. Herein, we design and successfully synthesize a series of Co NPs which show high performance on hydrogenation of nitroarenes with both activity and chemoselectivity. Co@C/PC preferentially activates the -C═O bond over -NO in water with ammonia borane (AB); however, when the hydrogen source is changes to hydrazine hydrate (HH), the results are the opposite. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00385DOI Listing

Controllable Eu-Doped Orthophosphate Blue-/Red-Emitting Phosphors: Charge Compensation and Lattice-Strain Control.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry , Chinese Academy of Sciences , Changchun 130022 , P. R. China.

Cation-substitution-induced controllable luminescence tuning could efficiently optimize and improve the luminescence performances of novel phosphor materials for realizing high-quality lighting. As important members of the orthophosphate family, ABPO (A = alkali metal Li, Na, K, Rb, Cs; B = alkali earth metal Mg, Ca, Sr, Ba) offers an abundant cation lattice environment for rare earth ions. Herein, we successfully prepared a broad-band red-emitting CsMgPO:Eu phosphor with an emission peak at 628 nm (fwhm = 118 nm). Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00577
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http://dx.doi.org/10.1021/acs.inorgchem.9b00577DOI Listing
April 2019
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NaMnSe: Strongly Frustrated Antiferromagnetic Semiconductor with Complex Magnetic Structure.

Inorg Chem 2019 Apr 23. Epub 2019 Apr 23.

Department of Chemistry and Biochemistry , Florida State University , Tallahassee , Florida 32306 , United States.

A new ternary selenide, NaMnSe, was prepared by a stoichiometric reaction between NaSe and metallic Mn at 923 K. Crystal structure determination revealed a new structure type, built of alternating layers of Na ions and [MnSe] anionic slabs. Band structure calculations indicate that NaMnSe is an indirect band gap semiconductor with E = 1. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00134DOI Listing

Halide-Free and Bifunctional One-Component Catalysts for the Coupling of Carbon Dioxide and Epoxides.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Chemistry and BK21+ Program Research Team , Chungbuk National University , Cheongju , Chungbuk 28644 , Republic of Korea.

In this paper, we first report a new class of halide-free and bifunctional one-component catalysts for the coupling of CO with epoxides. The catalysts do not need halide-based additives or tethered salts attached to the ligand when used for this coupling reaction. As the halide-free and bifunctional one-component catalysts, we chose nonionic and monomeric tetracarbonylchromium(0), tetracarbonylmolybdenum(0), and tetracarbonyltungsten(0) complexes chelated by modified ethylenediamines, namely N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N, N'-trimethylethylenediamine, and N, N, N', N'-tetramethylethylenediamine. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00262DOI Listing

Stabilizing Terminal Ni(III)-Hydroxide Complex Using NNN-Pincer Ligands: Synthesis and Characterization.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Chemistry , Indian Institute of Technology Bombay , Powai - 400076 , Mumbai , Maharashtra , India.

The reaction of [Ni(COD)] (COD; cyclooctadiene) in THF with the NNN-pincer ligand bis(imino)pyridyl (L) reveals a susceptibility to oxidation in an inert atmosphere ([O] level <0.5 ppm), resulting in a transient Ni:dioxygen adduct. This reactive intermediate abstracts a hydrogen atom from THF and stabilizes an uncommon Ni(III) complex. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00466DOI Listing

Law and Disorder: Special Stacking Units-Building the Intergrowth CeCoGe.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Center for Nanophysics and Advanced Materials, Department of Physics , University of Maryland , College Park , Maryland 20742 , United States.

A new structure type of composition CeCoGe was grown out of a molten Sn flux. CeCoGe crystallizes in the orthorhombic space group Cmcm, with highly anisotropic lattice parameters of a = 4.3293(5) Å, b = 55. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00350DOI Listing

Structures, Single-Molecule Magnets, and Fluorescent Properties of Four Dinuclear Lanthanide Complexes Based on 4-Azotriazolyl-3-hydroxy-2-naphthoic Acid.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Guangzhou Key Laboratory for Environmentally Functional Materials and Technology, School of Chemistry and Chemical Engineering , Guangzhou University , Guangzhou 510006 , P. R. China.

Four isostructural dinuclear lanthanide complexes based on 4-azotriazolyl-3-hydroxy-2-naphthoic acid (HATNA) and 3-hydroxy-2-naphthoic acid (HNA) ligands, {[Ln(HATNA)(HNA)(HO)]·6DMF} (Ln = Dy (1), Tb (2), Sm (3), Eu (4); DMF = N, N-dimethylformamide) have been prepared and characterized by X-ray diffraction crystallography, dc/ac magnetic characterization, and fluorescent spectrometry. The crystallographic data reveal dinuclear lanthanide cores of complexes 1-4, bridged by phenoxo and μ carboxyl groups. Each nine-coordinated Ln(III) ion is located in a slightly distorted monocapped square antiprism. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00260DOI Listing

Surface, Subsurface, and Bulk Oxygen Vacancies Quantified by Decoupling and Deconvolution of the Defect Structure of Redox-Active Nanoceria.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

School of Materials Science and Engineering, Faculty of Science , UNSW Sydney , Sydney , NSW 2052 , Australia.

Oxygen vacancy concentrations are critical to the redox/photocatalytic performance of nanoceria, but their direct analysis is problematic under controlled atmospheres but essentially impossible under aqueous conditions. The present work provides three novel approaches to analyze these data from XPS data for the three main morphologies of nanoceria synthesized under aqueous conditions and tested using in vacuo analytical conditions. First, the total oxygen vacancy concentrations are decoupled quantitatively into surface-filled, subsurface-unfilled, and bulk values. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00330DOI Listing

BiMoO Microsphere with Double-Polyaniline Layers toward Ultrastable Lithium Energy Storage by Reinforced Structure.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

College of Chemistry and Chemical Engineering , Central South University , Changsha 410083 , China.

Given its competitive theoretical capacity, BiMoO is deemed as a promising anode material for the realization of efficient Li storage. Considering the severe capacity attenuation caused by the lithiation-induced expansion, it is essential to introduce effective modification. Remarkably, in this work, BiMoO microsphere with double-layered spherical shells are successfully prepared, and the polyaniline are coated on both inner and outer surfaces of double-layered spherical shells, working as buffer layers to strain the volume expansion during electrochemical cycling. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00627DOI Listing

Synthesis, Spectroscopy, and Theoretical Details of Uranyl Schiff-Base Coordination Complexes.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Chemistry and Biochemistry , Florida State University , 95 Chieftan Way, Room 118 DLC , Tallahassee , Florida 32306 , United States.

Two uranyl Schiff-base coordination complexes, UOL(MeOH) and UOCl(HL) {L = N, N'-bis[(4,4'-diethylamino)salicylidene]-1,2-phenylenediamine}, have been synthesized that feature a rigid phenyl backbone. These complexes have been characterized by structural, spectroscopic, and theoretical analysis to offer an electronic structure basis to explain the bonding parameters and stability. Single-crystal X-ray analysis reveals that UOL(MeOH) adopts the typical "soft taco confirmation" characteristic of uranyl salophen complexes, whereas UOCl(HL) features an unusual neutral ligand coordination that contains an internal hydrogen bond between the phenol and imine. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00477DOI Listing

Insights on the Stability and Cationic Nonstoichiometry of CuFeO Delafossite.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

CIRIMAT , Université de Toulouse, CNRS, Université Paul Sabatier , 118 Route de Narbonne , 31062 Toulouse, Cedex 9 , France.

CuFeO, the structure prototype of the delafossite family, has received renewed interest in recent years. Thermodynamic modeling and several experimental Cu-Fe-O system investigations did not focus specifically on the possible nonstoichiometry of this compound, which is, nevertheless, a very important optimization factor for its physicochemical properties. In this work, through a complete set of analytical and thermostructural techniques from 50 to 1100 °C, a fine reinvestigation of some specific regions of the Cu-Fe-O phase diagram under air was carried out to clarify discrepancies concerning the delafossite CuFeO stability region as well as the eutectic composition and temperature for the reaction L = CuFeO + CuO. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00651
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http://dx.doi.org/10.1021/acs.inorgchem.9b00651DOI Listing
April 2019
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Two-Dimensional Zeolitic Imidazolate Framework-L-Derived Iron-Cobalt Oxide Nanoparticle-Composed Nanosheet Array for Water Oxidation.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

College of Food Science and Engineering , Northwest A&F University , 22 Xinong Road , Yangling 712100 , Shaanxi , China.

Rational design of various functional nanomaterials using MOFs as a template provides an effective strategy to synthesize electrocatalysts for water splitting. In this work, we reported that an iron-cobalt oxide with 2D well-aligned nanoflakes assembling on carbon cloth (Fe-CoO NS/CC), fabricated by an anion-exchange reaction followed by an annealing process, could serve as a high-performance oxygen-evolving catalyst. Specifically, the zeolitic imidazolate framework-L-Co nanosheet array (ZIF-L-Co NS/CC) was synthesized through a facile ambient liquid-phase deposition reaction, and then reacted with [Fe(CN)] ions as precursors during the anion-exchange reaction at room temperature. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00463DOI Listing

Competing Allosteric Mechanisms for Coordination-Directed Conformational Changes of Chiral Stacking Structures with Aromatic Rings.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Applied Chemistry , Tokyo University of Science , 1-3 Kagurazaka , Shinjuku-ku , Tokyo 162-8061 , Japan.

This work revealed that significant asymmetric nonlinear effects can be found in a coordination-directed conformational alteration through competing allosteric mechanisms. Toward this aim, we have prepared new chiral bridging ligands [( S, S)- and ( R, R)-ImAn] containing an anthracene ring as a spacer with two ethynyl-linked chiral imidazole groups at the 9,10-positions. The ( S, S)- and ( R, R)-ImAn ligands (L) spontaneously form the assemblies with Zn ions (M) in solution phase, giving LM-type assemblies with a general formula [( S, S)- or ( R, R)-ImAn](Zn). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00665DOI Listing

Stabilizing Reactive Fe(III) Clusters by Freeze-Dry/Solvent-Exchange To Benchmark Iron Hydrolysis Pathways.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Chemistry , Oregon State University , 153 Gilbert Hall , Corvallis , Oregon 97331 , United States.

Isolating Fe(III) clusters from water without stabilizing ligands is significantly challenged by the high acidity of Fe-bound water, leading to uncontrolled precipitation of iron oxyhydroxides. Here we demonstrate a freeze-drying solvent-exchange method that enabled the isolation of a metastable Fe(III) sulfate decameric cluster formulated [FeO(SO)(OCH)]·14CHOH (Fe). Without stabilization by solvent-exchange, the aqueous species undergoes rapid conversion to the iron sulfate mineral schwertmannite. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03446DOI Listing

Chiroptical Activity of Type II Core/Shell CuS/CdSe Nanocrystals.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Tianjin Key Laboratory of Applied Catalysis Science and Technology, School of Chemical Engineering and Technology , Tianjin University , Tianjin 300354 , People's Republic of China.

Ligand-induced chirality in core/shell nanocrystals (NCs) has attracted extensive attention because of many valuable potential applications. However, the cause of chirality especially in semiconductor nanomaterials is still under debate despite the creation of chiral type I core/shell structures. Herein, we synthesized a kind of new CuS/CdSe core/shell nanostructure to study the underlying reason. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00769
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http://dx.doi.org/10.1021/acs.inorgchem.9b00769DOI Listing
April 2019
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Oxygen Vacancies of Cr-Doped CeO Nanorods That Efficiently Enhance the Performance of Electrocatalytic N Fixation to NH under Ambient Conditions.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

College of Material Science and Engineering , Sichuan University , Chengdu 610064 , China.

Producing ammonia (NH) by electrocatalytic N fixation is a promising and environmentally friendly strategy, in comparison to the Haber-Bosch process with high consumption of energy and CO emissions. Because of the extremely high bond energy, it is indispensable to explore valid catalysts to activate the triple bond. In this paper, Cr-doped CeO nanorods are developed to serve as non-noble-metal electrocatalysts for an electrocatalytic N reduction reaction. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00622DOI Listing

Cobalt(II) Coordination Polymers Assembled from Unexplored Pyridine-Carboxylic Acids: Structural Diversity and Catalytic Oxidation of Alcohols.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Centro de Química Estrutural, Instituto Superior Técnico , Universidade de Lisboa , Av. Rovisco Pais , 1049-001 , Lisbon , Portugal.

New coordination polymers of cobalt(II), namely, [Co(μ-cpna)(HO)] (1), [Co(μ-cpna)(phen)(HO)] · nHO (2), [Co(μ-dppa)(HO)] ·2 nHO (3), and [Co(μ-dppa)(μ-4,4'-bipy)(HO)] ·4 nHO (4), have been generated under hydrothermal conditions from CoCl·6HO, two different multifunctional pyridine-carboxylic acids {Hcpna: 5-(4-carboxyphenoxy)nicotinic acid; Hdppa: 5-(3,4-dicarboxylphenyl)picolinic acid}, and optional N, N-supporting ligands {phen: 1,10-phenanthroline; 4,4'-bipy: 4,4'-bipyridine} acting as mediators of crystallization. These Co(II) coordination polymers (CPs) have been obtained as stable crystalline materials and characterized by conventional solid-state techniques, including X-ray crystallography. The obtained products are 3D metal-organic frameworks (MOFs 1 and 4) or 2D coordination polymers (CPs 2 and 3). Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00242DOI Listing

"Mr. Boron", an Inorganic Chemistry Icon, Turns 90.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Chemistry Department , Metropolitan State University of Denver , P.O. Box 173362, Campus Box 52 , Denver , Colorado 80217 , United States.

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http://dx.doi.org/10.1021/acs.inorgchem.9b00913DOI Listing

An Atomistic Understanding of the Unusual Thermal Behavior of the Molecular Oxide TcO.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Department of Chemistry and Biochemistry , University of Nevada Las Vegas , Las Vegas , Nevada 89154 , United States.

The thermal behavior of TcO has been investigated by single-crystal X-ray diffraction of the solid state over a range of 80-280 K and by ab initio molecular dynamics (MD) simulations. The thermal expansion coefficient of the solid was experimentally determined to be 189 × 10 Å K at 280 K. The simulations accurately reproduce the experimentally determined crystal structures and thermal expansion within a few percent. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b02368DOI Listing

Complexation of U(VI) with BiPDA, DmBiPDA, and PhenDA: Comparison on Structures and Binding Strengths in Aqueous and DMSO/20%(v)HO Solutions.

Inorg Chem 2019 Apr 22. Epub 2019 Apr 22.

Chemical Sciences Division , Lawrence Berkeley National Laboratory , Berkeley , California 94720 , United States.

The stability constants (log β) of 1:1 uranyl complexes with three N,O-mixed donor ligands (L = 2,2'-dipyridyl-6,6'-dicarboxylate, 3,3'-dimethyl-2,2'-bipyridine-6,6'-dicarboxylate, and 1,10-phenanthroline-2,9-dicarboxylate, denoted as BiPDA, DmBiPDA, and PhenDA, respectively) in aqueous and DMSO/20%(v)HO solutions were determined by spectrophotometry in 0.1 M tetraethylammonium perchlorate. The effects of ligand preorganization, steric hindrance, and solvation on the binding strength of U(VI) with the three ligands were discussed. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00319DOI Listing

Square Planar Cobalt(II) Hydride versus T-Shaped Cobalt(I): Structural Characterization and Dihydrogen Activation with PNP-Cobalt Pincer Complexes.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Anorganisch Chemisches Institut , Universität Heidelberg , Im Neuenheimer Feld 270 , Heidelberg 69120 , Germany.

The carbazole-based pincer ligand (PNP)H (R = Pr, Bu) has been used for the synthesis and characterization of various low- and high-spin cobalt complexes. Upon treatment of the high-spin complexes (PNP)CoCl (2-CoCl) with NaHBEt, the selective formation of cobalt(II) hydride 3 -CoH and T-shaped cobalt(I) complex 4 -Co was observed, depending on the substituents at the phosphorus atoms. For an unambiguous characterization of the reaction products, a density functional theory (DFT) supported paramagnetic NMR analysis was carried out, which established the electron configuration and the oxidation states of the metal atoms, thus demonstrating the significant impact of ligand substitution on the outcome of the reaction. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00384
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http://dx.doi.org/10.1021/acs.inorgchem.9b00384DOI Listing
April 2019
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Diamondoid Frameworks via Supramolecular Coordination: Structural Characterization, Metallogel Formation, and Adsorption Study.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Department of Chemistry , University of Utah , Salt Lake City , Utah 84112 , United States.

Supramolecular coordination has been developed as an efficient tool to construct a variety of discrete metallacycles and metallacages with well-defined shapes and sizes. However, its application in framework construction has been barely exploited. In this paper, we report the direct synthesis of two diamondoid frameworks from a simple tetrahedral precursor, tetra(4-(4-pyridinyl)phenyl)methane, and two linear difunctional platinum(II) ligands via one-step supramolecular coordination. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00484DOI Listing
April 2019
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In Situ Ligand Transformation for Two-Step Spin Crossover in Fe[M(CN)] (M = Mo, Nb) Cyanido-Bridged Frameworks.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Department of Chemistry, School of Science , The University of Tokyo , 7-3-1 Hongo , Bunkyo-ku, Tokyo 113-0033 , Japan.

We report a unique synthetic route toward the multistep spin crossover (SCO) effect induced by utilizing the partial ligand transformation during the crystallization process, which leads to the incorporation of three different Fe complexes into a single coordination framework. The 3-acetoxypyridine (3-OAcpy) molecules were introduced to the self-assembled Fe-[M(CN)] (M = Mo, Nb) system in the aqueous solution which results in the partial hydrolysis of the ligand into 3-hydroxypyridine (3-OHpy). It gives two novel isostructural three-dimensional {Fe(3-OAcpy)(3-OHpy)[M(CN)]}· nHO (M = Mo, n = 0, FeMo; M = Nb, n = 1, FeNb) coordination frameworks. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00361
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http://dx.doi.org/10.1021/acs.inorgchem.9b00361DOI Listing
April 2019
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Cu-F Interactions between Cationic Linear N-Heterocyclic Carbene Copper(I) Pyridine Complexes and Their Counterions Greatly Enhance Blue Luminescence Efficiency.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Faculty for Chemistry and Chemical Biology , TU Dortmund University , Otto-Hahn-Strasse 6 , 44227 Dortmund , Germany.

A series of easily accessible linear N-heterocyclic carbene (NHC) copper(I) complexes, bearing pyridine (py) and its derivatives as chromophore ligands, are barely emissive in the single-crystalline solid state. However, their powders, neat films, and dilute doped films of poly(methyl methacrylate) (PMMA; 1-10%) show very intense blue-to-blue-green photoluminescence with remarkable quantum yields φ of up to 87% and microsecond lifetimes, indicative of triplet states being involved. These luminescence properties are similar to trigonal coordinated NHC copper(I) bis(pyridine) complexes, which we have also isolated and characterized with respect to their structures and photophysics. Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00337
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http://dx.doi.org/10.1021/acs.inorgchem.9b00337DOI Listing
April 2019
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Maximizing Property Tuning of Phosphorus Corrole Photocatalysts through a Trifluoromethylation Approach.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Schulich Faculty of Chemistry , Technion-Israel Institute of Technology , Haifa 32000 , Israel.

An eight-member series of CF-substituted difluorophosphorus corroles was prepared for establishing a structure-activity profile of these high-potential photosensitizers. It consisted of preparing all four possible isomers of the monosubstituted corrole and complexes with 2-, 3-, 4-, and 5-CF groups on the macrocycle's periphery. The synthetic pathway to these CF-substituted derivatives, beginning with (tpfc)PF, involves two different initial routes: (i) direct electrophilic CF incorporation using FSOCFCOMe and copper iodide, or (ii) bromination to achieve the 2,3,8,17,18-pentabrominated compound using excess bromine in methanol. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.9b00436DOI Listing
April 2019
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Molecular Design of Cyclopentadienyl Tantalum Sulfide Complexes.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

Use of (MeSi)S and [Ta(η-CMe)Cl] (1) in a 4:3 ratio afforded the trimetallic sulfide cluster [Ta(η-CMe)Cl(μ-Cl)(μ-S)(μ-S)] (2) with loss of SiClMe. A similar reaction between 1, TaCl, and (MeSi)S in a 2:1:4 ratio resulted in the analogous complex [Ta(η-CMe)Cl(μ-Cl)(μ-S)(μ-S)] (3). Single-crystal X-ray diffraction analyses of 2 and 3 showed in all cases trinuclear tantalum sulfide clusters. Read More

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http://dx.doi.org/10.1021/acs.inorgchem.8b03563DOI Listing

Shedding Light on the Intrinsic Characteristics of 3D Distorted Fluorite-Type Zirconium Tellurite Single Crystals.

Inorg Chem 2019 Apr 19. Epub 2019 Apr 19.

State Key Laboratory of Crystal Materials , Shandong University , Jinan , Shandong 250100 , People's Republic of China.

Transition-metal tellurites have motivated growing research interest in both fundamental and applied chemistry, and the corresponding single crystals could serve as rich and fascinating platforms to regulate, explore, and elucidate the intrinsic characteristics of different structures from 0D to 3D architectures. In this context, a zirconium tellurite (namely, ZrTeO) single crystal featuring a 3D distorted fluorite-type structure with a size of 35 × 32 × 21 mm was successfully harvested by the top-seeded solution growth (TSSG) technique. The X-ray diffraction rocking curve reflects that the crystallinity of the as-grown ZrTeO crystal is quite perfect with a small full-width at half-maximum (fwhm) value (∼39 arcsec). Read More

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http://pubs.acs.org/doi/10.1021/acs.inorgchem.9b00424
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http://dx.doi.org/10.1021/acs.inorgchem.9b00424DOI Listing
April 2019
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